几个新型杂多钨酸盐的合成及晶体结构
|
摘要
本论文利用水热合成技术,通过含氮有机配体、抗衡离子及过渡金属离子的调变制备了九个新的杂多钨酸盐,并对这些化合物进行了元素分析、IR和单晶X-射线衍射表征,同时也对部分化合物的固态漫反射光谱性质、热稳定性、荧光光谱性质和磁学性质进行了研究。
1.采用配体2,2’-联吡啶和1,2-环己二胺,合成了两例基于三缺位[AsW9O34]9-单元构建的有机-无机砷钨酸盐：
H2[{Cu(2,2'-bpy)}8(H2O)2(AsW9O34)2]·12H2O(1)
(NH4)3[Ni(C6H,4N2)2]3[Ni(C6H15N2)Ni(H2O)Ni2(AsW9O34)2]·3H2O(2)
在化合物1中,两个三缺位多阴离子[a-AsW9O34]9-通过Cu3-O键桥连形成二聚结构,它是第一例基于[a-AsW9O34]9-阴离子的连接八个铜配合物的砷钨酸盐。化合物2是一例新的含有四核有机镍[Ni4(C6H15N2)(H2O)]单元的夹心型砷钨酸盐。
2.采用不同的配体,合成了五例基于饱和Keggin离子构建的有机-无机多金属氧酸盐：
[Co(2,2'-bpy)3]2[AsWⅤWⅥ11040]·3H2O(3)
[Co(2,2'-bpy)3][HAsW12040]-8H2O(4)
[Ni(C6H14N2)2]3[AsWⅤ3WⅥ9O40] (5)
[4,4'-H2bpy]H[Co(imi)4(AsCo(imi)W11O39)](6)
[Co(2,2'-bpy)3]1.5[Co(2,2'-bpy)2(H20)SiWⅤWⅥ11O40]·0.5H2O(7)
化合物3,4和5中,不同数目的过渡金属络离子与Keggin离子间主要通过静电引力和氢键相互作用；在化合物6中,Co(imi)单取代Keggin离子的一个端氧向过渡金属络离子配位形成了Keggin离子单支撑的有机-无机杂化化合物,进而由金属配合物[Co(imi)4桥连相邻多阴离子形成一维链状结构；化合物7为饱和Keggin离子单支撑的有机-无机杂化化合物,进而通过氢键形成一维双股链状结构。
3.以4,4’-联吡啶和咪唑为混配体,水热合成和结构表征了一例新型3D拓展结构的有机-无机Dawson型砷钨酸盐：
Cu18(imi)4(bpy)6(H2O)[AsⅤ2WⅤ2WⅥ16O62]·2H2O(8)
化合物8具有5-连接的氮化硼拓扑,拓扑符号为(46·64)。化合物8中多阴离子作为七齿无机配体与周围的七个过渡金属离子配位,显示了到目前为止修饰的Dawson型砷钨酸盐的最高连接。
4.通过抗衡离子的调节,合成了一例铜取代的夹心型砷钨酸盐：
Na(H2O)6Cu(H2O)4(NH4)6[Cu3.5(NH4)2(H2O)4(AsW9O33)2]·5H2O(9)
化合物9的杂多阴离子为夹心型结构,两个[ASW9O33]9-建筑单元间含有一个新的[Cu3.5(NH4)2(H2O)4]中心单元,每个夹心型杂多阴离子均通过四个Cu-O-W键连接了与其相邻的四个多阴离子形成二维网络结构。
In this paper, nine new polyoxometalates were synthesized under the hydrothermal conditions by adjusting organic N-donor ligands, counter ions and transition-metal ions, all of which were characterized by elemental analysis, IR and single crystal X-ray diffraction. Some of these compounds were characterized by UV-vis diffuse reflectance spectrum, fluorescent spectrum, thermal anelysis or magnetic measurement.
1. Two new inorganic-organic tungstoarsenates on the basis of trivacant Keggin ion [ASW9O34]9- have been hydrothermally synthesized by using organic ligands 2,2'-bpy or 1,2-diaminocyclohexane:
H2[{Cu(2,2'-bpy)}8(H2O)2(AsW9O34)2]-12H2O(1)
(NH4)3[Ni(C6H14N2)2]3[Ni(C6H15N2)Ni(H2O)Ni2(AsW9O34)2]·3H2O(2)
In compound 1, two trivacant polyanions [a-AsW9O34]9- are connected via Cu-O to form a centrosymmetric dimer, on which eight-copper-complexed were connected. Compound 2 is a new sandwich tungstoarsenate constructed from two trivacant polyanions [ASW9O34]9-linked through an unique [Ni4(C6H15N2)(H2O)] unit.
2. Five new inorganic-organic hybrids based saturated Keggin or monosubtituted Keggin polyoxometaltates have been hydrothermally synthesized by using different organic ligands:
[Co(2,2'-bpy)3]2[AsWⅤWⅥ11O40]-3H20(3)
[Co(2,2'-bpy)3][HAsW12O40]-8H2O(4)
[Ni(C6H14N2)2]3[AsWⅤ3WⅥ9O40] (5)
[4,4'-H2bpy]H[Co(imi)4(AsCo(imi)W11O39)](6)
[Co(2,2'-bpy)3]1.5[Co(2,2'-bpy)2(H2O)SiWⅤWⅥ11O40]-0.5H2O(7)
In compounds 3,4 and 5, the main interactions between metal complexes and saturated Keggin ions are hydrogen bond and electrostatic interaction; compound 6 is a Co(imi) gruop monosubtituted Keggin compound, and further covalently connected by [Co(imi)4] units to a one-dimensional chain; in compound 7, the saturated Keggin ion coordinates to Co(2,2'-bpy)2(H2O)2+ to form a monosupporting hybrid, furthmore linked by hydrogen bond to a 1D chain structure.
3. A novel inorganic-organic Dawson-type tungstoarsenate has been synthesized by introducing mixed organic ligands 4,4'-bpy and imidazole under the hydrothermal conditions and structurally characterized:
CuI8(imi)4(bpy)6(H2O)[AsⅤ2WⅤ2WⅥ16O62]-2H2O(8)
The compound 8 exhibits a five-connected boron nitride topology with the Schlafli symbol (46·64), in which Dawson polyanoin as hepta-dentate inorganic ligands coordinates with seven metal ions, representing the highest connecting number of modifying Dawson POMs.
4. A new copper-substituted sandwich tungstoarsenate has been hydrothermally synthesized by adjusting different counter ions:
Na(H2O)6Cu(H2O)4(NH4)6[Cu3.5(NH4)2(H2O)4(AsW9O33)2]-5H2O(9)
Compound 9 consists of two [ASW9O33]9- moieties linked by a new [Cu3.5(NH4)2(H2O)4] unit, and it is connected to four neighbors via four Cu-O-W bonds to form 2D network structure.
1.采用配体2,2’-联吡啶和1,2-环己二胺,合成了两例基于三缺位[AsW9O34]9-单元构建的有机-无机砷钨酸盐：
H2[{Cu(2,2'-bpy)}8(H2O)2(AsW9O34)2]·12H2O(1)
(NH4)3[Ni(C6H,4N2)2]3[Ni(C6H15N2)Ni(H2O)Ni2(AsW9O34)2]·3H2O(2)
在化合物1中,两个三缺位多阴离子[a-AsW9O34]9-通过Cu3-O键桥连形成二聚结构,它是第一例基于[a-AsW9O34]9-阴离子的连接八个铜配合物的砷钨酸盐。化合物2是一例新的含有四核有机镍[Ni4(C6H15N2)(H2O)]单元的夹心型砷钨酸盐。
2.采用不同的配体,合成了五例基于饱和Keggin离子构建的有机-无机多金属氧酸盐：
[Co(2,2'-bpy)3]2[AsWⅤWⅥ11040]·3H2O(3)
[Co(2,2'-bpy)3][HAsW12040]-8H2O(4)
[Ni(C6H14N2)2]3[AsWⅤ3WⅥ9O40] (5)
[4,4'-H2bpy]H[Co(imi)4(AsCo(imi)W11O39)](6)
[Co(2,2'-bpy)3]1.5[Co(2,2'-bpy)2(H20)SiWⅤWⅥ11O40]·0.5H2O(7)
化合物3,4和5中,不同数目的过渡金属络离子与Keggin离子间主要通过静电引力和氢键相互作用；在化合物6中,Co(imi)单取代Keggin离子的一个端氧向过渡金属络离子配位形成了Keggin离子单支撑的有机-无机杂化化合物,进而由金属配合物[Co(imi)4桥连相邻多阴离子形成一维链状结构；化合物7为饱和Keggin离子单支撑的有机-无机杂化化合物,进而通过氢键形成一维双股链状结构。
3.以4,4’-联吡啶和咪唑为混配体,水热合成和结构表征了一例新型3D拓展结构的有机-无机Dawson型砷钨酸盐：
Cu18(imi)4(bpy)6(H2O)[AsⅤ2WⅤ2WⅥ16O62]·2H2O(8)
化合物8具有5-连接的氮化硼拓扑,拓扑符号为(46·64)。化合物8中多阴离子作为七齿无机配体与周围的七个过渡金属离子配位,显示了到目前为止修饰的Dawson型砷钨酸盐的最高连接。
4.通过抗衡离子的调节,合成了一例铜取代的夹心型砷钨酸盐：
Na(H2O)6Cu(H2O)4(NH4)6[Cu3.5(NH4)2(H2O)4(AsW9O33)2]·5H2O(9)
化合物9的杂多阴离子为夹心型结构,两个[ASW9O33]9-建筑单元间含有一个新的[Cu3.5(NH4)2(H2O)4]中心单元,每个夹心型杂多阴离子均通过四个Cu-O-W键连接了与其相邻的四个多阴离子形成二维网络结构。
In this paper, nine new polyoxometalates were synthesized under the hydrothermal conditions by adjusting organic N-donor ligands, counter ions and transition-metal ions, all of which were characterized by elemental analysis, IR and single crystal X-ray diffraction. Some of these compounds were characterized by UV-vis diffuse reflectance spectrum, fluorescent spectrum, thermal anelysis or magnetic measurement.
1. Two new inorganic-organic tungstoarsenates on the basis of trivacant Keggin ion [ASW9O34]9- have been hydrothermally synthesized by using organic ligands 2,2'-bpy or 1,2-diaminocyclohexane:
H2[{Cu(2,2'-bpy)}8(H2O)2(AsW9O34)2]-12H2O(1)
(NH4)3[Ni(C6H14N2)2]3[Ni(C6H15N2)Ni(H2O)Ni2(AsW9O34)2]·3H2O(2)
In compound 1, two trivacant polyanions [a-AsW9O34]9- are connected via Cu-O to form a centrosymmetric dimer, on which eight-copper-complexed were connected. Compound 2 is a new sandwich tungstoarsenate constructed from two trivacant polyanions [ASW9O34]9-linked through an unique [Ni4(C6H15N2)(H2O)] unit.
2. Five new inorganic-organic hybrids based saturated Keggin or monosubtituted Keggin polyoxometaltates have been hydrothermally synthesized by using different organic ligands:
[Co(2,2'-bpy)3]2[AsWⅤWⅥ11O40]-3H20(3)
[Co(2,2'-bpy)3][HAsW12O40]-8H2O(4)
[Ni(C6H14N2)2]3[AsWⅤ3WⅥ9O40] (5)
[4,4'-H2bpy]H[Co(imi)4(AsCo(imi)W11O39)](6)
[Co(2,2'-bpy)3]1.5[Co(2,2'-bpy)2(H2O)SiWⅤWⅥ11O40]-0.5H2O(7)
In compounds 3,4 and 5, the main interactions between metal complexes and saturated Keggin ions are hydrogen bond and electrostatic interaction; compound 6 is a Co(imi) gruop monosubtituted Keggin compound, and further covalently connected by [Co(imi)4] units to a one-dimensional chain; in compound 7, the saturated Keggin ion coordinates to Co(2,2'-bpy)2(H2O)2+ to form a monosupporting hybrid, furthmore linked by hydrogen bond to a 1D chain structure.
3. A novel inorganic-organic Dawson-type tungstoarsenate has been synthesized by introducing mixed organic ligands 4,4'-bpy and imidazole under the hydrothermal conditions and structurally characterized:
CuI8(imi)4(bpy)6(H2O)[AsⅤ2WⅤ2WⅥ16O62]-2H2O(8)
The compound 8 exhibits a five-connected boron nitride topology with the Schlafli symbol (46·64), in which Dawson polyanoin as hepta-dentate inorganic ligands coordinates with seven metal ions, representing the highest connecting number of modifying Dawson POMs.
4. A new copper-substituted sandwich tungstoarsenate has been hydrothermally synthesized by adjusting different counter ions:
Na(H2O)6Cu(H2O)4(NH4)6[Cu3.5(NH4)2(H2O)4(AsW9O33)2]-5H2O(9)
Compound 9 consists of two [ASW9O33]9- moieties linked by a new [Cu3.5(NH4)2(H2O)4] unit, and it is connected to four neighbors via four Cu-O-W bonds to form 2D network structure.
引文
[1]王恩波,胡长文,许林.多酸化学导论[M].北京：化学工业出版社,1997：1
[2]王恩波,胡长文,许林.多酸化学导论[M].北京：化学工业出版社,1998：125-137
[3]Pauling L., The molecular structure of the tungstosilicates and related compounds[J]. Journal of the American Chemical Society,1929, V51(10):2868-2880
[4]Keggin J.F., Structure of the crystals of 12-phosphotungstic acid[J]. Nature,1933, V132: 351
[5]Maayan G, Biro R.P., Neumann R., Micelle directed synthesis of polyoxometalate nanoparticles and their improved catalytic activity for the aerobic oxidation of sulfides[J]. Journal of the American Chemical Society,2006, V128(15):4968-4969
[6]Noro S.I., Tsunasnima R., Kamiya Y., et al. Adsorption and catalytic properties of the inner nanospace of a gigantic ring-shaped polyoxometalate cluster[J]. Angewandte Chemie. International Edition,2009, V48(46):8703-8706
[7]Kreutz J.E., Shukhaev A., Du W., et al. Evolution of Catalysts Directed by Genetic Algorithns in a Plug-Based Microfluidic Device Tested with Oxidation of Methane by Oxygen[J]. Journal of the American Chemical Society,2010, V132(9):3128-3132
[8]Barnard D.L., Hill C.L., Gage T., et al. Potent inhibition of respiratory syncytial virus by polyoxometalates of several structural classes[J]. Antiviral Research,1997, V34(1):27-37
[9]Hill C.L., Weeks M.S., Schinazi R.F., Anti-HIV-1 activity, toxicity, and stability studies of representative structural families of polyoxometalates[J]. Journal of Medicinal Chemistry, 1990, V33(10):2767-2772
[10]Truflandier L.A., Autschbach J., Probing the Solvent Shell with 195Pt Chemical Shifts: Density Functional Theory Molecular Dynamics Study of PtⅡ and PtⅣ Anionic Complexes in Aqueous Solution[J]. Journal of the American Chemical Society,2010, V132 (10):3472-3483
[11]Rodriguez-Albelo L.M., Ruiz-Salvador A.R., Sampieri A., et al. Zeolitic Polyoxometalate-Based Metal-Organic Frameworks (Z-POMOFs):Computational Evaluation of Hypothetical Polymorphs and the Successful Targeted Synthesis of the Redox-Active Z-POMOF1[J]. Journal of the American Chemical Society,2009, V131 (44):16078-16087
[12]Hardwick A., Dickens P.G., Slade R.C.T., Investigation of proton motion in the 21-hydrates of 12-tungstophosphoric and 12-molybdophosphoric acids by a.c. conductivity and pulsed proton NMR measurements[J]. Solid State Ionics,1984, V13(4): 345-350
[13]Compain J.D., Mialane P., Dolbecq A., et al. Iron Polyoxometalate Single-Molecule Magnets[J]. Angewandte Chemie. International Edition,2009, V48(17):3077-3081
[14]Aldamen M.A., Clemente-Juan J.M., Coronado E., et al. Mononuclear Lanthanide Single-Molecule Magnets Based on Polyoxometalates[J]. Journal of the American Chemical Society,2008, V130(28):8874-8875
[15]Mǖller A., Krickemeyer E., Meyer J., et al. [Mo154(No)140420(OH)28(H20)70](25±5)-:a water-soluble big wheel with more than 700 atoms and a relative molecular mass of about 24,000[J]. Angewandte Chemie. International Edition,1995, V34(19):2122-2124
[16]Miiller A., Krickemeyer E., Bogge H., et al. Formation of a ring-shaped reduced "Metal Oxide" with the simple composition [(MoO3)176(H20)80H32][J]. Angewandte Chemie. International Edition,1998,V37(9):1220-1222
[17]Wassermann K., Dickman M.H., Pope M.T., Self-Assembly of Supramolecular Polyoxometalates:The Compact, Water-Soluble Heteropolytungstate Anion [As12ⅢCe16Ⅲ(H2O)36W148O524]76-[J]. Angewandte Chemie. International Edition,1997, V36(13):1445-1448
[18]Mǖller A., Beckmann E., Bogge H., et al. Inorganic chemistry goes protein size:a Mo368 nano-hedgehog initiating nanochemistry by symmetry breaking[J]. Angewandte Chemie. International Edition,2002, V41(7):1162-1167
[19]Bi L.H., Kortz U., Synthesis and structure of the pentacopper (II) substituted tungstosilicate [Cu5(OH)4(H2O)2(A-a-SiW9O33)2]10-[J]. Inorganic Chemistry,2004, V43(25):7961-7962
[20]Bi L.H., Kortz U., Nellutla S., et al. Structure, electrochemistry, and magnetism of the Iron(Ⅲ)-substituted Keggin dimer, [Fe6(OH)3(A-a-GeW9O34(OH)3)2]11-[J]. Inorganic Chemistry,2005, V44(4):896-903
[21]Anderson T.M., Neiwert W.A., Hill C.L., Multi-iron silicotungstates:synthesis, characterization, and stability studies of polyoxometalate dimers[J]. Inorganic Chemistry, 2004, V43(23):7353-7358
[22]Zhang Z.M., Li Y.G., Wang E.B., et al. Synthesis, characterization, and crystal structures of two novel high-nuclear nickel-substituted dimeric polyoxometalates[J]. Inorganic Chemistry,2006, V45(11):4313-4315
[23]Yamase T., Fukaya K., Nojiri H., et al. Ferromagnetic exchange interactions for Cu612+ and Mn612+ hexagons sandwiched by two B-α-[XW9O33]9-(X= AsⅢ and SbⅢ) ligands in D3d-symmetric polyoxotungstates[J]. Inorganic Chemistry,2006, V45(19):7698-7704
[24]Chang S., Qi Y.F., Wang E.B., et al. Two novel sandwiched-type polyoxotungstates containing Zn6 transition-metal cluster: Syntheses, structures and luminescent property[J]. Inorganica Chimica Acta,2009, V362(2):453-457
[25]Tan H.Q., Zhang Z.M., Liu D., et al. A New Sandwich Polyoxometalate Constructed from a Zn612+ Hexagon Cluster Sandwiched by Two B-a-[BiW9O33]9-[J]. Journal of Cluster Science,2008,19:545-550
[26]Zhao Z.F., Zhou B.B., Zheng S.T., et al. Hydrothermal synthesis, crystal structure and magnetic characterization of three hexa-M substituted tungstoarsenates (M= Ni, Zn and Mn)[J]. Inorganica Chimica Acta,2009, V362(14):5038-5042
[27]Yao S., Zhang Z.M., Li Y.G., et al. A{Cu6}-containing inorganic-metal-organic sandwich-type tungstoantimonite and its 3D supramolecular framework[J]. Inorganic Chemistry Communications,2009, V12(10):937-940
[28]Zheng S.T., Yuan D.Q., Zhang J., et al. Combination of lacunary polyoxometalates and high-nuclear transition metal clusters under hydrothermal conditions.3. structure and characterization of [Cu(enMe)2]2{[Cu(enMe)2(H2O)2][Cu6(enMe)2(B-α-SiW9O34)2]·4H2O[J].Inorganic Chemistry,2007, V46(11):4569-4574
[29]Zhang Z.M., Wang E.B., Qi Y.F., et al. Synthesis, characterization, and crystal structures of double-cubane-substituted and asymmetric penta-Ni-substituted dimeric polyoxometalates[J]. Crystal Growth & Design,2007, V7(7):1305-1311
[30]Lisnard L., Mialane P., Dolbecq A., et al. Effect of Cyanato, Azido, Carboxylato, and Carbonato Ligands on the Formation of Cobalt(Ⅱ) Polyoxometalates:Characterization, Magnetic, and Electrochemical Studies of Multinuclear Cobalt Clusters[J]. Chemistry-A European Journal.2007, V13(12):3525-3536
[31]Zhao J.W., Wang C.M., Zhang J., et al. Combination of Lacunary Polyoxometalates and High-Nuclear Transition Metal Clusters under Hydrothermal Conditions:IX. A Series of Novel Polyoxotungstates Sandwiched by Octa-Copper Clusters[J]. Chemistry-A European Journal.2008, V14(30):9223-9239
[32]Plchon C., Mlalane P., Dolbecq A., et al. Octa- and nonanuclear nickel(II) polyoxometalate clusters:synthesis and electrochemical and magnetic characterizations [J]. Inorganic Chemistry,2008, V47(23):11120-11128
[33]Wang J.P., Duan X.Y., Du X.D., et al. Novel Rare Earth Germanotungstates and Organic Hybrid Derivatives:Synthesis and Structures of M/[a-GeW11O39] (M) Nd, Sm, Y, Yb) and Sm/[a-GeW11O39](DMSO)[J]. Crystal Growth & Design,2006, V6(10):2266-2270
[34]Sadakane M., Dickman M.H., Pope M.T., Controlled assembly of polyoxometalate chains from lacunary building blocks and lanthanide-cation linkers[J]. Angewandte Chemie. International Edition,2000, V36(16):3914-2916
[35]Chen L.L., Zhang L., Gao Y.R., et al. Two extended organic-inorganic hybrids based on sandwich tungstogermanates[J]. Journal of Coordination Chemistry,2009, V62(17): 2832-2841
[36]Ritchie C., Burkholder E.M., Long D.L., et al. Exploiting the multifunctionality of organocations in the assembly of hybrid polyoxometalate clusters and networks [J]. Chemical Communications,2007, (5):468-470
[37]Alizadeh M.H., Eshtiagh-Hosseini H., Khoshnavazi R., Synthesis, structure, and characterization of a new sandwich-type arsenotungstocerate, [As2W18Ce3O71(H2O)3]2-[J]. Journal of Molecular Structure,2004, V688(1-3):33-39
[38]Khoshnavazi R., Salimi A., Moaser A.G., Complexes with carbonate as a tridentate ligand:Synthesis and characterization of sandwich-type polyoxometallates [(A-a-AsW9O34)2(MOH2)3(CO3)]11 (M= Y(Ⅲ), Yb(Ⅲ) and Sm(Ⅲ))[J]. Polyhedron,2008, V27(4):1303-1309
[39]Khoshnavazi R., Bahrami L., Tin derivatives of A-a-AsW9O349-:Synthesis and characterization of [Sn3Ⅱ(A-a-AsW9O34)2]12-, [(PhSnⅣOH)3(A-a-AsW9O34)2]12- and [(HOSnⅣOH)3(AsW9O34)2]12- [J]. Journal of Coordination Chemistry,2009, V62(13): 2067-2075
[40]Evans H.T., Tourne C.M., Tourne G.F., et al. X-Ray crystallographic and tungsten-183 nuclear magnetic resonance structural studies of the [M4(H2O)2(XW9O34)2]10-heteropolyanions (M= CoⅡ or Zn, X=P or As)[J]. Journal of the Chemical Society Dalton Transaction,1986, (12):2699-2705
[41]Bi L.H., Huang R.D., Peng J., et al. Rational syntheses, characterization, crystal structure, and replacement reactions of coordinated water molecules of [As2W18M4(H2O)2O68]10-(M= Cd, Co, Cu, Fe, Mn, Ni or Zn)[J]. Journal of the Chemical Society Dalton Transaction,2001, (24):121-129
[42]Rosu C., Crans D.C., Weakley T.J.R., Rational synthesis and X-ray structure of [MnⅡ4(H2O)2(AsⅤW9O34)2]10- from [AsⅢW40O140]28-, MnO4- and Mn2+[J]. Polyhedron, 2002, V21(9-10):959-962
[43]Dan R., Cora C., Mariana R., et al. Complexes of the trilacunary Keggin arseno(Ⅴ)polyoxotungstate with iron(Ⅲ), cobalt(Ⅱ) and nickel(Ⅱ)[J]. Rom. Revue Roumaine de Chimie,2007, V52(8-9),817-821
[44]Daniel D., Melanie L.E., Bernt K., Synthesis and crystal structure of the tetra-nickel substituted [Ni4(H2O)2(AsW9O34)2]10-polyoxoanion[J]. Zeitschrift fuer Naturforschung, B:Chemical Sciences,2004, V59(9):980-984
[45]Hussain F., Bi L.H., Rauwald U., er al. Structure and solution properties of the cadmium(II)-substituted tungstoarsenate[Cd4Cl2(B-α-AsW9O34)2]12-[J].Polyhedron,2005, V24(7):847-852
[46]Wang J.P., Wang W., Niu J.Y., A novel sandwich polyoxometalate linked by mixed RE/TM interlayer:[Fe(phen)3]2[As2W18Fe2{Y(OH2)2}2O68]·6.5H2O[J]. Journal of Molecular Structure,2008, V873(1-3):29-34
[47]Khoshnavazi R., Kaviani L., Zonoz F.M., Dioxouranium complexes as ligand. Synthesis and characterization of sandwich-type polyoxometalates [X2W18(UO2)2{(H2O)3M}2O68]10-(X=AsⅤand PⅤ)(M= CoⅡ, CuⅡ, MnⅡ, NiⅡand ZnⅡ)[J]. Inorganica Chimica Acta,2009, V362(4):1223-1228
[48]Mbomekalle I.M., Keita B., Nierlich M., et al. Structure, Magnetism, and Electrochemistry of the Multinickel Polyoxoanions [Ni6As3W24O94(H2O)2]17-， [Ni3Na(H2O)2(AsW9O34)2]11-, and [Ni4Mn2P3W24O94(H2O)2]17-[J]. Inorganic Chemistry, 2003, V42(17):5143-5152
[49]Lu X.M., Liu B., Sarula et al. Synthesis, crystal structure and NMR of [Na(DB18C6)(CH3CN)]3[α-AsM1204o] (M=Mo/W)[J]. Inorganic Chemistry Communications,2005, V8(12):1133-1136
[50]Wang J.P., Wang W., Niu J.Y., Hydrothermal synthesis and crystal structure of a novel composite Keggin-type arsenotungstate:[Ni(phen)2][Hphen](AsW12040)[J].Chinese Journal of Structure Chemistry,2007, V26(2):194-198
[51]Yi Z.H., Cui X.B., Zhang X., et al. Hydrothermal syntheses and structures of two novel polyoxometalate-based 3-D supramolecular architectures[J]. Journal of Molecular Structure,2008, V891(1-3):123-128
[52]Li M.X., Niu Y.H., Wang W., et al. A Keggin-type Arsenotungstate Anion-supported Transition Metal Complex:Hydrothermal Synthesis and Characterization of [Fe(2,2'-bipy)3]1.5[AsWⅥ10WⅤ204oFe(2,2'-bipy)2(H2O)]-0.25H2O[J]. Zeitschrift fur Naturforschung,2008, V63b:183-186
[53]Zhao J.W., Han Q.X., Ma P.T., et al. A CdSO4-like 3-D framework constructed from monosodium substituted Keggin arsenotungstates and copper(Ⅱ)-ethylenediamine complexes[J], Inorganic Chemistry Communications,2009, V12(8):707-710
[54]Wang J.P., Wang W., Niu J.Y., Self-assembly of [β-As(V)W8O31]9- subunit in hydrothermal system with moderate acidity:Synthesis, crystal structure and characterizations of dimeric arsenotungstate H2[{Cu(phen)}8(β-AsW8O31)2] · 2.5H2O [J]. Inorganic Chemistry Communications,2007, V10(9):1054-1057
[55]Chen L.J., Zhao J.W., Ma P.T., et al. An organic-inorganic hybrid nickel-substituted arsenotungstate consisting of three types of polyoxotungstate units[J]. Inorganic Chemistry Communications,2010, V13(1):50-53
[56]Wang Y.H., Hu C.W., Peng J., et al. Synthesis, characterization and X-ray crystal structure of a novel polyoxotungstoarsenate: K6[{Cu(β-Ala)2(H2O)2}2{Cu4(H2O)2(AsW9O34)2}]·17H2O (β-Ala=β-alanine)[J]. Journal of Molecular Structure,2001, V598(2-3):161-169
[57]Fan L.L., Wang E.B., Li Y.G., et al. Wells-Dawson anion, a useful building block to construct one-dimensional chain as a chelate ligand coordinating with transition metal cations[J]. Journal of Molecular Structure,2007, V841(1-3):28-33
[58]Yi Z.H., Cui X.B., Zhang X., et al.A novel 2D layer structure constructed from sandwich-type transition metal substituted tungstates and nickel coordination fragments: [Ni(enMe)2]2[Ni(enMe)2(H2O)]2[As2W18Ni4(enMe)2O68]·2H3O·2H2O[J]. Journal of Molecular Structure,2008, V885(1-3):149-153
[59]衣智慧.新的金属氧簇的设计合成与结构表征[D].吉林：吉林大学,2007
[60]Bi L.H., Hou G.F., Wu L.X., et al. An organo-ruthenium grafted zinc-substituted tungstoarsenate[J]. Crystal Engineering Communications,2009, V11(8):1532-1535
[61]Ma P.T., Zhao J.W., Wang J.P., et al. Sandwich-type polyoxometalate hybrids decorated by nickel-aromatic amine complexes[J]. Journal of Solid State Chemistry,2010, V183(1): 150-156
[62]Wang J.P., Wang W., Liu Y.H., et al. Synthesis, crystal structure and characterization of a polyoxometalate containing a novel 1D polycation chain: [{M(2,2'-bipy)}5O14]4[2,2'-H2bipy]2(As2W18O62)2-8H2O (M=Mo, W)[J]. Acta Chimica Sinica,2007, V65(17):1826-1830
[63]Wang J.P., Wang W., Niu J.Y., Hydrothermal syntheses, characterizations and crystal structures of 1-D and 2-D arsenotungstates based on Dawson-type units[J]. Journal of Molecular Structure,2008, V875 (1-3):68-74
[64]Yang D., Yu L., Wang W., et al. Hydrothermal synthesis and crystal structure of [J]. Journal of Henan University (Natural Science),2008, V38(2):148-152
[65]Yao F., Meng F.X., Chen Y.G., et al. Two organic-inorganic hybrids based on polyoxometalates:synthesis, crystal structure, and characterization[J]. Journal of Coordination Chemistry,2010, V63(2):196-205
[66]Yamase T., Naruke H., Sasaki Y., Crystallographic characterization of the polyoxotungstate [Eu3(H2O)3(SbW9O33)(W5O18)3]18- and energy transfer in its crystalline lattices[J]. Journal of the Chemical Society Dalton Transaction,1990, (5):1687-1696
[67]陈义平,赵士龙,张汉辉等.三种具有Keggin结构的硅钨氧簇化合物的光谱研究[J].光谱学与光谱分析,2004,V24(3)：257-260
[68]Li S.L., Lan Y.Q., Ma J.F., et al. Structures and Luminescent Properties of Seven Coordination Polymers of Zinc(II) and Cadmium(II) with 3,3',4,4'-Benzophenone Tetracarboxylate Anion and Bis(imidazole)[J]. Crystal Growth & Design,2008, V8(2): 675-684
[69]Luo Z., Kogerler P., Cao R., et al. Synthesis, structure and magnetism of a new dimeric silicotungstate:K9Na2Cu0.5[y-Cu2(H20)SiW8O31]2·38H20[J]. Journal of the Chemical Society Dalton Transaction,2008, (1):54-58
[70]Luo Z., Kogerler P., Cao R., et al. Synthesis, structure and magnetism of a one-dimensional silicotungstate array: K3H4Cuo.5{Cu[Cu7.5Si2W1606o(H20)4(OH)4]2}·9H2O[J]. Polyhedron,2009, V28(2): 215-220
[71]Zhang H.M., Li Y.G., Lu Y., et al. A New Ni12 Cluster Based on Polyoxometalate Ligands[J]. Inorganic Chemistry,2009, V48(23):10889-10891
[72]Brown I.D., in: M. O'Keeffe and A. Navrotsky (Ed.), Structure and Bonding in Crystals, vol.11, Academic Press, New York,1981, pp.1-30
[73]Khan M.I., Cevik S., Doedens R.J., et al. Hydrothermal synthesis and characterization of mixed-valence hexatungstates:crystal structures of [(C2Hs)4N]3[WⅤW5ⅥO19]-0.5H2O and [H3N(CH2)2NH3]2[WⅤW5ⅥO19]·[H2N(CH2)2NH2]Cl·8H2O[J]. Inorganica Chimica Acta,1998, V277(1):69-75
[74]Pope M.T., Miiller A., Polyoxometalate Chemistry: An Old Field with New Dimensions in Several Disciplines[J]. Angewandte Chemie. International Edition,1991, V30(1): 34-48
[75]Gamelas J.A.F., Cavaleiro A.M.V., Gomes E.de M., et al. Synthesis, properties and photochromism of novel charge transfer compounds with Keggin anions and protonated 2,2'-biquinoline[J]. Polyhedron, V21(25-26):2537-2545
[76]Chen W.L., Chen B.W., Li Y.G., et al. Two new extended frameworks constructed from the sandwiching polytungstoarsenate clusters[J]. Inorganica Chimica Acta,2009, V362 (14):5043-5054
[77]Mulliken R.S. Molecular compounds and their spectra. Ⅱ[J]. Journal of the American Chemical Society,1952, V74(3):811-824
[78]Mulliken R.S., Person W.B. Molecular Complexes[M]. A Lecture and Reprint Volume; Wiley:New York,1969:2-5
[79]Sun H.L., Ma B.Q., Gao S., et al. A Novel Three-Dimensional Network Containing Mn(II) Ions and Tricyanomethanide with Rare 46-64 Topology[J]. Crystal Growth & Design,2005, V5(4):1331-1333
[80]Liu C.M., Zhang D.Q., Zhu D.B.,3D Supramolecular Array Assembled by Cross-like Arrangement of ID Sandwich Mixed Molybdenum-Vanadium Polyoxometalate Bridged Coordination Polymer Chains:Hydrothermal Synthesis and Crystal Structure of {[MoⅥ5MoⅤ3VⅣ8O40(P04)][Ni(en)2]}[Ni(en)2]2-4H20 [J]. Crystal Growth & Design, 2005, V5(4):1639-1642
[81]Liu C.M., Luo J.L., Zhang D.Q., et al. Spin Glass Behaviour in a 1D Mixed Molybdenum-Vanadium Heteropolyoxometalate-Bridged Coordination Polymer[J]. European Journal of Inorganic Chemistry,2004, (24):4774-4779
[82]Jin H., Qi Y.F., Xiao D.R., et al. Two novel inorganic-organic hybrids based on saturated Wells-Dawson polyoxoanion and copper-organonitrogen coordination polymer [J]. Journal of Molecular Structure,2007, V837(1-3):23-29
[83]Acerete R., Hammer C.F., Baker L.C.W., Reinterpretations, based on tungsten-183 NMR spectra, of several heteropolytungstates derived from the Wells-Dawson "2:18" structure. Preparation and structure proof for the first.gamma.-isomer of a 2:18 complex[J]. Inorganic Chemistry,1984, V23(10):1478-1482
[84]Zheng X.F., Zhou Y.X., Wan X.S., Syntheses, crystal structures and properties of two novel supramolecular complexes with a-Thiophene Carboxylate, [Pb(phen)(tpa)2] and [Cu(im)2(tpa)2H2O] (phen=1,10-phenanthroline, tpa= thiophene carboxylic acid, im= imidazole)[J]. Synthesis and Reactivity in Inorganic, Metal-Organic and Nano-Metal Chemistry,2007, V37:255-261
[85]Kortz U., Al-Kassem N.K., Savelieff M.G., et al. Synthesis and Characterization of Copper-, Zinc-, Manganese-, and Cobalt-Substituted Dimeric Heteropolyanions, [(a-XW9O33)2M3(H2O)3]n" (n= 12, X= AsⅢ, ⅢM= Cu2+, Zn2+; n= 10, X= SeⅣ, TeIV, M= Cu2+) and [(α-AsW9O33)2WO(H2O)M2(H2O)2]10- (M= Zn2+, Mn2+, Co2+)[J]. Inorganic Chemistry,2001, V40(18):4742-4749
[86]Mialane P., Marrot J., Riviere E., et al. Structural Characterization and Magnetic Properties of Sandwich-Type Tungstoarsenate Complexes. Study of a Mixed-Valent VⅣ2/VⅤ Heteropolyanion[J]. Inorganic Chemistry,2001, V40(18):44-48
[87]Kortz U., Nellutla S., Stowe A.C., et al. Structure and Magnetism of the Tetra-Copper(Ⅱ)-Substituted Heteropolyanion [Cu4K2(H2O)8(α-AsW9O33)2] 8-[J]. Inorganic Chemistry,2004, V43(1):144-154
[88]Bi L.H., Li B., Wu L.X., et al. Synthesis, characterization and crystal structure of a novel 2D network structure based on hexacopper(Ⅱ) substituted tungstoantimonate[J]. Inorganica Chimica Acta,2009, V362(9):3309-3313
[89]Pichon C., Mialane P., Dolbecq A., et al. Characterization and Electrochemical Properties of Molecular Icosanuclear and Bidimensional Hexanuclear Cu(Ⅱ) Azido Polyoxometalates[J]. Inorganic Chemistry,2007, V46(13):5292-5301
[90]Xu H.S., Li L.L., Liu B., et al. AsMo7O27-Bridged Dinuclear Sandwich-Type Heteropolymolybdates of Cr(Ⅲ) and Fe(Ⅲ):Magnetism of [MM'(AsMo7O27)2]12-with MM'= FeFe, CrFe, and CrCr[J]. Inorganic Chemistry,2009, V48(21):10275-10280
[2]王恩波,胡长文,许林.多酸化学导论[M].北京：化学工业出版社,1998：125-137
[3]Pauling L., The molecular structure of the tungstosilicates and related compounds[J]. Journal of the American Chemical Society,1929, V51(10):2868-2880
[4]Keggin J.F., Structure of the crystals of 12-phosphotungstic acid[J]. Nature,1933, V132: 351
[5]Maayan G, Biro R.P., Neumann R., Micelle directed synthesis of polyoxometalate nanoparticles and their improved catalytic activity for the aerobic oxidation of sulfides[J]. Journal of the American Chemical Society,2006, V128(15):4968-4969
[6]Noro S.I., Tsunasnima R., Kamiya Y., et al. Adsorption and catalytic properties of the inner nanospace of a gigantic ring-shaped polyoxometalate cluster[J]. Angewandte Chemie. International Edition,2009, V48(46):8703-8706
[7]Kreutz J.E., Shukhaev A., Du W., et al. Evolution of Catalysts Directed by Genetic Algorithns in a Plug-Based Microfluidic Device Tested with Oxidation of Methane by Oxygen[J]. Journal of the American Chemical Society,2010, V132(9):3128-3132
[8]Barnard D.L., Hill C.L., Gage T., et al. Potent inhibition of respiratory syncytial virus by polyoxometalates of several structural classes[J]. Antiviral Research,1997, V34(1):27-37
[9]Hill C.L., Weeks M.S., Schinazi R.F., Anti-HIV-1 activity, toxicity, and stability studies of representative structural families of polyoxometalates[J]. Journal of Medicinal Chemistry, 1990, V33(10):2767-2772
[10]Truflandier L.A., Autschbach J., Probing the Solvent Shell with 195Pt Chemical Shifts: Density Functional Theory Molecular Dynamics Study of PtⅡ and PtⅣ Anionic Complexes in Aqueous Solution[J]. Journal of the American Chemical Society,2010, V132 (10):3472-3483
[11]Rodriguez-Albelo L.M., Ruiz-Salvador A.R., Sampieri A., et al. Zeolitic Polyoxometalate-Based Metal-Organic Frameworks (Z-POMOFs):Computational Evaluation of Hypothetical Polymorphs and the Successful Targeted Synthesis of the Redox-Active Z-POMOF1[J]. Journal of the American Chemical Society,2009, V131 (44):16078-16087
[12]Hardwick A., Dickens P.G., Slade R.C.T., Investigation of proton motion in the 21-hydrates of 12-tungstophosphoric and 12-molybdophosphoric acids by a.c. conductivity and pulsed proton NMR measurements[J]. Solid State Ionics,1984, V13(4): 345-350
[13]Compain J.D., Mialane P., Dolbecq A., et al. Iron Polyoxometalate Single-Molecule Magnets[J]. Angewandte Chemie. International Edition,2009, V48(17):3077-3081
[14]Aldamen M.A., Clemente-Juan J.M., Coronado E., et al. Mononuclear Lanthanide Single-Molecule Magnets Based on Polyoxometalates[J]. Journal of the American Chemical Society,2008, V130(28):8874-8875
[15]Mǖller A., Krickemeyer E., Meyer J., et al. [Mo154(No)140420(OH)28(H20)70](25±5)-:a water-soluble big wheel with more than 700 atoms and a relative molecular mass of about 24,000[J]. Angewandte Chemie. International Edition,1995, V34(19):2122-2124
[16]Miiller A., Krickemeyer E., Bogge H., et al. Formation of a ring-shaped reduced "Metal Oxide" with the simple composition [(MoO3)176(H20)80H32][J]. Angewandte Chemie. International Edition,1998,V37(9):1220-1222
[17]Wassermann K., Dickman M.H., Pope M.T., Self-Assembly of Supramolecular Polyoxometalates:The Compact, Water-Soluble Heteropolytungstate Anion [As12ⅢCe16Ⅲ(H2O)36W148O524]76-[J]. Angewandte Chemie. International Edition,1997, V36(13):1445-1448
[18]Mǖller A., Beckmann E., Bogge H., et al. Inorganic chemistry goes protein size:a Mo368 nano-hedgehog initiating nanochemistry by symmetry breaking[J]. Angewandte Chemie. International Edition,2002, V41(7):1162-1167
[19]Bi L.H., Kortz U., Synthesis and structure of the pentacopper (II) substituted tungstosilicate [Cu5(OH)4(H2O)2(A-a-SiW9O33)2]10-[J]. Inorganic Chemistry,2004, V43(25):7961-7962
[20]Bi L.H., Kortz U., Nellutla S., et al. Structure, electrochemistry, and magnetism of the Iron(Ⅲ)-substituted Keggin dimer, [Fe6(OH)3(A-a-GeW9O34(OH)3)2]11-[J]. Inorganic Chemistry,2005, V44(4):896-903
[21]Anderson T.M., Neiwert W.A., Hill C.L., Multi-iron silicotungstates:synthesis, characterization, and stability studies of polyoxometalate dimers[J]. Inorganic Chemistry, 2004, V43(23):7353-7358
[22]Zhang Z.M., Li Y.G., Wang E.B., et al. Synthesis, characterization, and crystal structures of two novel high-nuclear nickel-substituted dimeric polyoxometalates[J]. Inorganic Chemistry,2006, V45(11):4313-4315
[23]Yamase T., Fukaya K., Nojiri H., et al. Ferromagnetic exchange interactions for Cu612+ and Mn612+ hexagons sandwiched by two B-α-[XW9O33]9-(X= AsⅢ and SbⅢ) ligands in D3d-symmetric polyoxotungstates[J]. Inorganic Chemistry,2006, V45(19):7698-7704
[24]Chang S., Qi Y.F., Wang E.B., et al. Two novel sandwiched-type polyoxotungstates containing Zn6 transition-metal cluster: Syntheses, structures and luminescent property[J]. Inorganica Chimica Acta,2009, V362(2):453-457
[25]Tan H.Q., Zhang Z.M., Liu D., et al. A New Sandwich Polyoxometalate Constructed from a Zn612+ Hexagon Cluster Sandwiched by Two B-a-[BiW9O33]9-[J]. Journal of Cluster Science,2008,19:545-550
[26]Zhao Z.F., Zhou B.B., Zheng S.T., et al. Hydrothermal synthesis, crystal structure and magnetic characterization of three hexa-M substituted tungstoarsenates (M= Ni, Zn and Mn)[J]. Inorganica Chimica Acta,2009, V362(14):5038-5042
[27]Yao S., Zhang Z.M., Li Y.G., et al. A{Cu6}-containing inorganic-metal-organic sandwich-type tungstoantimonite and its 3D supramolecular framework[J]. Inorganic Chemistry Communications,2009, V12(10):937-940
[28]Zheng S.T., Yuan D.Q., Zhang J., et al. Combination of lacunary polyoxometalates and high-nuclear transition metal clusters under hydrothermal conditions.3. structure and characterization of [Cu(enMe)2]2{[Cu(enMe)2(H2O)2][Cu6(enMe)2(B-α-SiW9O34)2]·4H2O[J].Inorganic Chemistry,2007, V46(11):4569-4574
[29]Zhang Z.M., Wang E.B., Qi Y.F., et al. Synthesis, characterization, and crystal structures of double-cubane-substituted and asymmetric penta-Ni-substituted dimeric polyoxometalates[J]. Crystal Growth & Design,2007, V7(7):1305-1311
[30]Lisnard L., Mialane P., Dolbecq A., et al. Effect of Cyanato, Azido, Carboxylato, and Carbonato Ligands on the Formation of Cobalt(Ⅱ) Polyoxometalates:Characterization, Magnetic, and Electrochemical Studies of Multinuclear Cobalt Clusters[J]. Chemistry-A European Journal.2007, V13(12):3525-3536
[31]Zhao J.W., Wang C.M., Zhang J., et al. Combination of Lacunary Polyoxometalates and High-Nuclear Transition Metal Clusters under Hydrothermal Conditions:IX. A Series of Novel Polyoxotungstates Sandwiched by Octa-Copper Clusters[J]. Chemistry-A European Journal.2008, V14(30):9223-9239
[32]Plchon C., Mlalane P., Dolbecq A., et al. Octa- and nonanuclear nickel(II) polyoxometalate clusters:synthesis and electrochemical and magnetic characterizations [J]. Inorganic Chemistry,2008, V47(23):11120-11128
[33]Wang J.P., Duan X.Y., Du X.D., et al. Novel Rare Earth Germanotungstates and Organic Hybrid Derivatives:Synthesis and Structures of M/[a-GeW11O39] (M) Nd, Sm, Y, Yb) and Sm/[a-GeW11O39](DMSO)[J]. Crystal Growth & Design,2006, V6(10):2266-2270
[34]Sadakane M., Dickman M.H., Pope M.T., Controlled assembly of polyoxometalate chains from lacunary building blocks and lanthanide-cation linkers[J]. Angewandte Chemie. International Edition,2000, V36(16):3914-2916
[35]Chen L.L., Zhang L., Gao Y.R., et al. Two extended organic-inorganic hybrids based on sandwich tungstogermanates[J]. Journal of Coordination Chemistry,2009, V62(17): 2832-2841
[36]Ritchie C., Burkholder E.M., Long D.L., et al. Exploiting the multifunctionality of organocations in the assembly of hybrid polyoxometalate clusters and networks [J]. Chemical Communications,2007, (5):468-470
[37]Alizadeh M.H., Eshtiagh-Hosseini H., Khoshnavazi R., Synthesis, structure, and characterization of a new sandwich-type arsenotungstocerate, [As2W18Ce3O71(H2O)3]2-[J]. Journal of Molecular Structure,2004, V688(1-3):33-39
[38]Khoshnavazi R., Salimi A., Moaser A.G., Complexes with carbonate as a tridentate ligand:Synthesis and characterization of sandwich-type polyoxometallates [(A-a-AsW9O34)2(MOH2)3(CO3)]11 (M= Y(Ⅲ), Yb(Ⅲ) and Sm(Ⅲ))[J]. Polyhedron,2008, V27(4):1303-1309
[39]Khoshnavazi R., Bahrami L., Tin derivatives of A-a-AsW9O349-:Synthesis and characterization of [Sn3Ⅱ(A-a-AsW9O34)2]12-, [(PhSnⅣOH)3(A-a-AsW9O34)2]12- and [(HOSnⅣOH)3(AsW9O34)2]12- [J]. Journal of Coordination Chemistry,2009, V62(13): 2067-2075
[40]Evans H.T., Tourne C.M., Tourne G.F., et al. X-Ray crystallographic and tungsten-183 nuclear magnetic resonance structural studies of the [M4(H2O)2(XW9O34)2]10-heteropolyanions (M= CoⅡ or Zn, X=P or As)[J]. Journal of the Chemical Society Dalton Transaction,1986, (12):2699-2705
[41]Bi L.H., Huang R.D., Peng J., et al. Rational syntheses, characterization, crystal structure, and replacement reactions of coordinated water molecules of [As2W18M4(H2O)2O68]10-(M= Cd, Co, Cu, Fe, Mn, Ni or Zn)[J]. Journal of the Chemical Society Dalton Transaction,2001, (24):121-129
[42]Rosu C., Crans D.C., Weakley T.J.R., Rational synthesis and X-ray structure of [MnⅡ4(H2O)2(AsⅤW9O34)2]10- from [AsⅢW40O140]28-, MnO4- and Mn2+[J]. Polyhedron, 2002, V21(9-10):959-962
[43]Dan R., Cora C., Mariana R., et al. Complexes of the trilacunary Keggin arseno(Ⅴ)polyoxotungstate with iron(Ⅲ), cobalt(Ⅱ) and nickel(Ⅱ)[J]. Rom. Revue Roumaine de Chimie,2007, V52(8-9),817-821
[44]Daniel D., Melanie L.E., Bernt K., Synthesis and crystal structure of the tetra-nickel substituted [Ni4(H2O)2(AsW9O34)2]10-polyoxoanion[J]. Zeitschrift fuer Naturforschung, B:Chemical Sciences,2004, V59(9):980-984
[45]Hussain F., Bi L.H., Rauwald U., er al. Structure and solution properties of the cadmium(II)-substituted tungstoarsenate[Cd4Cl2(B-α-AsW9O34)2]12-[J].Polyhedron,2005, V24(7):847-852
[46]Wang J.P., Wang W., Niu J.Y., A novel sandwich polyoxometalate linked by mixed RE/TM interlayer:[Fe(phen)3]2[As2W18Fe2{Y(OH2)2}2O68]·6.5H2O[J]. Journal of Molecular Structure,2008, V873(1-3):29-34
[47]Khoshnavazi R., Kaviani L., Zonoz F.M., Dioxouranium complexes as ligand. Synthesis and characterization of sandwich-type polyoxometalates [X2W18(UO2)2{(H2O)3M}2O68]10-(X=AsⅤand PⅤ)(M= CoⅡ, CuⅡ, MnⅡ, NiⅡand ZnⅡ)[J]. Inorganica Chimica Acta,2009, V362(4):1223-1228
[48]Mbomekalle I.M., Keita B., Nierlich M., et al. Structure, Magnetism, and Electrochemistry of the Multinickel Polyoxoanions [Ni6As3W24O94(H2O)2]17-， [Ni3Na(H2O)2(AsW9O34)2]11-, and [Ni4Mn2P3W24O94(H2O)2]17-[J]. Inorganic Chemistry, 2003, V42(17):5143-5152
[49]Lu X.M., Liu B., Sarula et al. Synthesis, crystal structure and NMR of [Na(DB18C6)(CH3CN)]3[α-AsM1204o] (M=Mo/W)[J]. Inorganic Chemistry Communications,2005, V8(12):1133-1136
[50]Wang J.P., Wang W., Niu J.Y., Hydrothermal synthesis and crystal structure of a novel composite Keggin-type arsenotungstate:[Ni(phen)2][Hphen](AsW12040)[J].Chinese Journal of Structure Chemistry,2007, V26(2):194-198
[51]Yi Z.H., Cui X.B., Zhang X., et al. Hydrothermal syntheses and structures of two novel polyoxometalate-based 3-D supramolecular architectures[J]. Journal of Molecular Structure,2008, V891(1-3):123-128
[52]Li M.X., Niu Y.H., Wang W., et al. A Keggin-type Arsenotungstate Anion-supported Transition Metal Complex:Hydrothermal Synthesis and Characterization of [Fe(2,2'-bipy)3]1.5[AsWⅥ10WⅤ204oFe(2,2'-bipy)2(H2O)]-0.25H2O[J]. Zeitschrift fur Naturforschung,2008, V63b:183-186
[53]Zhao J.W., Han Q.X., Ma P.T., et al. A CdSO4-like 3-D framework constructed from monosodium substituted Keggin arsenotungstates and copper(Ⅱ)-ethylenediamine complexes[J], Inorganic Chemistry Communications,2009, V12(8):707-710
[54]Wang J.P., Wang W., Niu J.Y., Self-assembly of [β-As(V)W8O31]9- subunit in hydrothermal system with moderate acidity:Synthesis, crystal structure and characterizations of dimeric arsenotungstate H2[{Cu(phen)}8(β-AsW8O31)2] · 2.5H2O [J]. Inorganic Chemistry Communications,2007, V10(9):1054-1057
[55]Chen L.J., Zhao J.W., Ma P.T., et al. An organic-inorganic hybrid nickel-substituted arsenotungstate consisting of three types of polyoxotungstate units[J]. Inorganic Chemistry Communications,2010, V13(1):50-53
[56]Wang Y.H., Hu C.W., Peng J., et al. Synthesis, characterization and X-ray crystal structure of a novel polyoxotungstoarsenate: K6[{Cu(β-Ala)2(H2O)2}2{Cu4(H2O)2(AsW9O34)2}]·17H2O (β-Ala=β-alanine)[J]. Journal of Molecular Structure,2001, V598(2-3):161-169
[57]Fan L.L., Wang E.B., Li Y.G., et al. Wells-Dawson anion, a useful building block to construct one-dimensional chain as a chelate ligand coordinating with transition metal cations[J]. Journal of Molecular Structure,2007, V841(1-3):28-33
[58]Yi Z.H., Cui X.B., Zhang X., et al.A novel 2D layer structure constructed from sandwich-type transition metal substituted tungstates and nickel coordination fragments: [Ni(enMe)2]2[Ni(enMe)2(H2O)]2[As2W18Ni4(enMe)2O68]·2H3O·2H2O[J]. Journal of Molecular Structure,2008, V885(1-3):149-153
[59]衣智慧.新的金属氧簇的设计合成与结构表征[D].吉林：吉林大学,2007
[60]Bi L.H., Hou G.F., Wu L.X., et al. An organo-ruthenium grafted zinc-substituted tungstoarsenate[J]. Crystal Engineering Communications,2009, V11(8):1532-1535
[61]Ma P.T., Zhao J.W., Wang J.P., et al. Sandwich-type polyoxometalate hybrids decorated by nickel-aromatic amine complexes[J]. Journal of Solid State Chemistry,2010, V183(1): 150-156
[62]Wang J.P., Wang W., Liu Y.H., et al. Synthesis, crystal structure and characterization of a polyoxometalate containing a novel 1D polycation chain: [{M(2,2'-bipy)}5O14]4[2,2'-H2bipy]2(As2W18O62)2-8H2O (M=Mo, W)[J]. Acta Chimica Sinica,2007, V65(17):1826-1830
[63]Wang J.P., Wang W., Niu J.Y., Hydrothermal syntheses, characterizations and crystal structures of 1-D and 2-D arsenotungstates based on Dawson-type units[J]. Journal of Molecular Structure,2008, V875 (1-3):68-74
[64]Yang D., Yu L., Wang W., et al. Hydrothermal synthesis and crystal structure of [J]. Journal of Henan University (Natural Science),2008, V38(2):148-152
[65]Yao F., Meng F.X., Chen Y.G., et al. Two organic-inorganic hybrids based on polyoxometalates:synthesis, crystal structure, and characterization[J]. Journal of Coordination Chemistry,2010, V63(2):196-205
[66]Yamase T., Naruke H., Sasaki Y., Crystallographic characterization of the polyoxotungstate [Eu3(H2O)3(SbW9O33)(W5O18)3]18- and energy transfer in its crystalline lattices[J]. Journal of the Chemical Society Dalton Transaction,1990, (5):1687-1696
[67]陈义平,赵士龙,张汉辉等.三种具有Keggin结构的硅钨氧簇化合物的光谱研究[J].光谱学与光谱分析,2004,V24(3)：257-260
[68]Li S.L., Lan Y.Q., Ma J.F., et al. Structures and Luminescent Properties of Seven Coordination Polymers of Zinc(II) and Cadmium(II) with 3,3',4,4'-Benzophenone Tetracarboxylate Anion and Bis(imidazole)[J]. Crystal Growth & Design,2008, V8(2): 675-684
[69]Luo Z., Kogerler P., Cao R., et al. Synthesis, structure and magnetism of a new dimeric silicotungstate:K9Na2Cu0.5[y-Cu2(H20)SiW8O31]2·38H20[J]. Journal of the Chemical Society Dalton Transaction,2008, (1):54-58
[70]Luo Z., Kogerler P., Cao R., et al. Synthesis, structure and magnetism of a one-dimensional silicotungstate array: K3H4Cuo.5{Cu[Cu7.5Si2W1606o(H20)4(OH)4]2}·9H2O[J]. Polyhedron,2009, V28(2): 215-220
[71]Zhang H.M., Li Y.G., Lu Y., et al. A New Ni12 Cluster Based on Polyoxometalate Ligands[J]. Inorganic Chemistry,2009, V48(23):10889-10891
[72]Brown I.D., in: M. O'Keeffe and A. Navrotsky (Ed.), Structure and Bonding in Crystals, vol.11, Academic Press, New York,1981, pp.1-30
[73]Khan M.I., Cevik S., Doedens R.J., et al. Hydrothermal synthesis and characterization of mixed-valence hexatungstates:crystal structures of [(C2Hs)4N]3[WⅤW5ⅥO19]-0.5H2O and [H3N(CH2)2NH3]2[WⅤW5ⅥO19]·[H2N(CH2)2NH2]Cl·8H2O[J]. Inorganica Chimica Acta,1998, V277(1):69-75
[74]Pope M.T., Miiller A., Polyoxometalate Chemistry: An Old Field with New Dimensions in Several Disciplines[J]. Angewandte Chemie. International Edition,1991, V30(1): 34-48
[75]Gamelas J.A.F., Cavaleiro A.M.V., Gomes E.de M., et al. Synthesis, properties and photochromism of novel charge transfer compounds with Keggin anions and protonated 2,2'-biquinoline[J]. Polyhedron, V21(25-26):2537-2545
[76]Chen W.L., Chen B.W., Li Y.G., et al. Two new extended frameworks constructed from the sandwiching polytungstoarsenate clusters[J]. Inorganica Chimica Acta,2009, V362 (14):5043-5054
[77]Mulliken R.S. Molecular compounds and their spectra. Ⅱ[J]. Journal of the American Chemical Society,1952, V74(3):811-824
[78]Mulliken R.S., Person W.B. Molecular Complexes[M]. A Lecture and Reprint Volume; Wiley:New York,1969:2-5
[79]Sun H.L., Ma B.Q., Gao S., et al. A Novel Three-Dimensional Network Containing Mn(II) Ions and Tricyanomethanide with Rare 46-64 Topology[J]. Crystal Growth & Design,2005, V5(4):1331-1333
[80]Liu C.M., Zhang D.Q., Zhu D.B.,3D Supramolecular Array Assembled by Cross-like Arrangement of ID Sandwich Mixed Molybdenum-Vanadium Polyoxometalate Bridged Coordination Polymer Chains:Hydrothermal Synthesis and Crystal Structure of {[MoⅥ5MoⅤ3VⅣ8O40(P04)][Ni(en)2]}[Ni(en)2]2-4H20 [J]. Crystal Growth & Design, 2005, V5(4):1639-1642
[81]Liu C.M., Luo J.L., Zhang D.Q., et al. Spin Glass Behaviour in a 1D Mixed Molybdenum-Vanadium Heteropolyoxometalate-Bridged Coordination Polymer[J]. European Journal of Inorganic Chemistry,2004, (24):4774-4779
[82]Jin H., Qi Y.F., Xiao D.R., et al. Two novel inorganic-organic hybrids based on saturated Wells-Dawson polyoxoanion and copper-organonitrogen coordination polymer [J]. Journal of Molecular Structure,2007, V837(1-3):23-29
[83]Acerete R., Hammer C.F., Baker L.C.W., Reinterpretations, based on tungsten-183 NMR spectra, of several heteropolytungstates derived from the Wells-Dawson "2:18" structure. Preparation and structure proof for the first.gamma.-isomer of a 2:18 complex[J]. Inorganic Chemistry,1984, V23(10):1478-1482
[84]Zheng X.F., Zhou Y.X., Wan X.S., Syntheses, crystal structures and properties of two novel supramolecular complexes with a-Thiophene Carboxylate, [Pb(phen)(tpa)2] and [Cu(im)2(tpa)2H2O] (phen=1,10-phenanthroline, tpa= thiophene carboxylic acid, im= imidazole)[J]. Synthesis and Reactivity in Inorganic, Metal-Organic and Nano-Metal Chemistry,2007, V37:255-261
[85]Kortz U., Al-Kassem N.K., Savelieff M.G., et al. Synthesis and Characterization of Copper-, Zinc-, Manganese-, and Cobalt-Substituted Dimeric Heteropolyanions, [(a-XW9O33)2M3(H2O)3]n" (n= 12, X= AsⅢ, ⅢM= Cu2+, Zn2+; n= 10, X= SeⅣ, TeIV, M= Cu2+) and [(α-AsW9O33)2WO(H2O)M2(H2O)2]10- (M= Zn2+, Mn2+, Co2+)[J]. Inorganic Chemistry,2001, V40(18):4742-4749
[86]Mialane P., Marrot J., Riviere E., et al. Structural Characterization and Magnetic Properties of Sandwich-Type Tungstoarsenate Complexes. Study of a Mixed-Valent VⅣ2/VⅤ Heteropolyanion[J]. Inorganic Chemistry,2001, V40(18):44-48
[87]Kortz U., Nellutla S., Stowe A.C., et al. Structure and Magnetism of the Tetra-Copper(Ⅱ)-Substituted Heteropolyanion [Cu4K2(H2O)8(α-AsW9O33)2] 8-[J]. Inorganic Chemistry,2004, V43(1):144-154
[88]Bi L.H., Li B., Wu L.X., et al. Synthesis, characterization and crystal structure of a novel 2D network structure based on hexacopper(Ⅱ) substituted tungstoantimonate[J]. Inorganica Chimica Acta,2009, V362(9):3309-3313
[89]Pichon C., Mialane P., Dolbecq A., et al. Characterization and Electrochemical Properties of Molecular Icosanuclear and Bidimensional Hexanuclear Cu(Ⅱ) Azido Polyoxometalates[J]. Inorganic Chemistry,2007, V46(13):5292-5301
[90]Xu H.S., Li L.L., Liu B., et al. AsMo7O27-Bridged Dinuclear Sandwich-Type Heteropolymolybdates of Cr(Ⅲ) and Fe(Ⅲ):Magnetism of [MM'(AsMo7O27)2]12-with MM'= FeFe, CrFe, and CrCr[J]. Inorganic Chemistry,2009, V48(21):10275-10280